EP2963145B1 - Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée - Google Patents

Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée Download PDF

Info

Publication number
EP2963145B1
EP2963145B1 EP15171849.1A EP15171849A EP2963145B1 EP 2963145 B1 EP2963145 B1 EP 2963145B1 EP 15171849 A EP15171849 A EP 15171849A EP 2963145 B1 EP2963145 B1 EP 2963145B1
Authority
EP
European Patent Office
Prior art keywords
cathode
metal
hipims
coating
power supply
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15171849.1A
Other languages
German (de)
English (en)
Other versions
EP2963145A1 (fr
Inventor
Papken E. Hovsepian
Dave Doerwald
Roel Tietema
Arutiun Papken Ehiasarian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IHI Hauzer Techno Coating BV
Original Assignee
IHI Hauzer Techno Coating BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IHI Hauzer Techno Coating BV filed Critical IHI Hauzer Techno Coating BV
Priority to EP15171849.1A priority Critical patent/EP2963145B1/fr
Priority to JP2015124446A priority patent/JP6636728B2/ja
Priority to US14/755,073 priority patent/US20150376532A1/en
Publication of EP2963145A1 publication Critical patent/EP2963145A1/fr
Application granted granted Critical
Publication of EP2963145B1 publication Critical patent/EP2963145B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04—Metals; Alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—Material
    • H01J37/3429—Plural materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target

Definitions

  • the present invention relates to a coating and to methods for its deposition, the coating being intended to operate in boundary lubrication conditions and at elevated temperatures.
  • Dynamic lubrication is frequently used in industry, in machines and in motor cars for the lubrication between two relatively moving components.
  • One example is the oil film that is present between a shell bearing and a crankshaft. The idea is to maintain an oil film between the two components so that the two relatively moving surfaces are not in physical contact. If physical contact occurs then the surfaces wear rapidly and mechanical damage or failure results.
  • the lubrication is inadequate so that asperities on the surface of one component rub on asperities of the other component, which may not be catastrophic but nevertheless leads to unwanted wear and reduced working life. Such situations can be summarised under the term "boundary lubrication"
  • boundary lubrication is the lubrication of piston rings which scrape over the running surface of a cylinder.
  • the lubrication of the piston rings is critical and can certainly be classed as a boundary lubrication condition. Even with adequate oil supply boundary lubrication conditions can arise elsewhere in a motor vehicle engine or in machinery generally.
  • boundary lubrication can for example arise between crankshafts and shell bearings, between camshafts and camshaft followers or between rocker arms and valve actuation mechanisms as well as in fuel injection systems to name but a few examples.
  • boundary lubrication the ideal situation of no real contact between rubbing partners is not met and contact can occur.
  • the problem becomes worse as operating temperatures rise.
  • piston ring temperatures up to 250° C or even 350°C can arise and as circulating oil is often at temperatures above 100°C corresponding component temperatures, e.g. in the area of the crankshaft and the valve train/cam train, are frequent.
  • DLC coating is an abbreviation for a diamond like carbon coating which contains predominantly sp3 carbon bonds and has a structure resembling diamond.
  • the coating which can be regarded as a benchmark coating for piston rings, is almost as hard as diamond. It is typically applied in a plasma assisted reactive chemical deposition process referred to as PACVD or PECVD. However this is relatively costly as the deposition rate is relatively slow. Furthermore DLC coatings suffer from poor adhesion due to their high stress and inefficient surface treatment prior to the coating deposition.
  • DE 10 2012 007 796 A is related to metal (Me) doped DLC coated sliding members, such as piston rings.
  • Me may be Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Ni, W.
  • W-doped DLC is disclosed as preferred embodiment.
  • the mean Me content is most preferably 5 to 20 at.%.
  • the principal object underlying the present invention is to provide a novel coating which can be applied cost effectively by PVD processes, which is entirely competitive with existing DLC coatings and indeed potentially superior especially at elevated temperatures under boundary lubrication conditions.
  • a coating of this kind is capable of providing low friction and low wear of the coated component and its running partner even under boundary lubrication conditions and at elevated temperatures. It has been surprisingly found that the claimed Me-doped carbon coating does not suffer from oxidation damage in dry air up to 500°C and outperform DLC coatings in lubricated sliding at elevated temperatures as high as 200°C. Metal DLC coatings are admittedly known per se but have always been considered inferior to DLC coatings. The applicants have found, to their surprise, that metal DLC coatings with the special percentage of 5 to 20 atomic percent of a mixture of Mo and W have enhanced efficiency in boundary lubrication conditions.
  • Metal contents in an amount above 20% by atomic percent are significantly poorer in performance than coatings with less than or equal to 20% by atomic percent. If the metal content is reduced below 5 atomic percent there seems to be insufficient metal in the coating for the beneficial effect to occur and endure over a long operating period.
  • the preferred proportion of the metal in atomic percent is in the range from 10 to 20%, with proportions near to 20% being especially preferred.
  • Both Mo and W are metals capable of forming a metal sulphide with sulphur present in a lubricant.
  • the applicants have evidence that conclusively shows that such metals do indeed react with the sulphur in the lubricant to form the metal sulphide and metal sulphides are known to be good solid lubricants per se.
  • the process of metal sulphide formation is enhanced at higher temperatures, such as those prevailing in internal combustion engines and at the surfaces of piston rings.
  • Particularly beneficial results are achieved when the mixture of W and Mo in a ratio in the range by atomic percent of W:Mo from 0.5:1 to 4:1 preferably from 1:1 to 3:1 and especially of about 2:1.
  • the performance of the coating at room temperature is comparable to that of pure DLC and is considerably better at elevated temperature, such as occur at piston ring surfaces.
  • the metal doped hard carbon coatings proposed here can operate at least at a temperature in the range from 0°C-500°C and have their best properties at higher temperatures above 150°C.
  • the typical range of useful thickness of the coatings proposed here is from 500nm to 10 ⁇ m and the typical hardness is in the range from12 GPa to20 GPa.
  • a method for depositing the metal doped hard carbon coating of the invention on a workpiece comprises the following method steps:
  • This method is particularly advantageous for a variety of reasons.
  • First of all it is basically a non-reactive sputtering process which does not involve any reactive gas, unless nitrogen is admitted to the vacuum chamber during the method step B) for the formation of a metal nitride transition layer, which is by no means essential but an option.
  • Magnetron sputtering is known to produce droplet free smooth layers, particularly when HIPIMS is used for sputtering.
  • the deposition of the carbon in the coating can be done simply by having enough carbon in a single composite cathode of WC and C, for example in the form of a segmented cathode or one made by powder metallurgy, or enough carbon in a single composite cathode of W and/or WC with Mo and C, for example again in the form of a segmented cathode or one made by powder metallurgy. It is however generally more convenient to provide at least one additional graphite cathode that is operated in addition to cathode configurations a), b) or c) in a DC sputtering mode.
  • three graphite cathodes each of 1200 square cm's area can be operated in a DC sputtering mode at 5 to 6KW of applied power.
  • the single target of WC and Mo with an area of 1200 square cm is also operated in a HIPIMS mode at an average power of 5 to 6 kW. If desired it could be operated at a higher average power.
  • the important thing is to achieve the correct proportion of metal in the coating by atomic percent.
  • the operation of the cathode configurations a), b) and c) in a HIPIMS mode has a particularly beneficial effect on the DC sputtering from the graphite cathodes. This namely results in the desired ratio of sp2 to sp3 bonds in the hard carbon coating. Since the Me and hard carbon coating is deposited in one step the process is very efficient and the production rate is relatively high compared to that of DLC coatings, about twice as high, which is another significant advantage.
  • the metal used for the adhesive layer can also be produced from the cathodes of the configurations a), b) or c) with the DC magnetrons from the graphite cathodes being inoperative during the method step B) as it is in the method step A).Since the same cathode configuration can be used for the steps B) and C) there is no need to provide a separate cathode for the method step B) and this saves considerable cost, again making the process attractive commercially.
  • At least the deposition step C) and optionally all method steps are carried out in an argon atmosphere in a vacuum treatment chamber at an argon pressure in the range from 1 to 10 -3 millibar to 10 -1 millibar and preferably at 3 x 10 -3 millibar.
  • the pre-treatment step A) is most preferably carried out using the method described in European patent EP 1 260 603
  • step A) is carried out using a HIPIMS power supply and any of the cathode configurations a), b) and c) and with a workpiece bias voltage higher than -500 volts and preferably of -1000 volts or greater.
  • the method steps B) and /or C) are carried out either with no separate bias voltage applied to the workpiece resulting in a floating bias potential of -30 to -40 volts or with a bias power supply connected to the workpiece and adapted to supply a bias voltage at the workpiece in the range from -30 volts to -200 volts.
  • bias power supply When a bias power supply is used this is preferably designed in accordance with the European PCT application published as WO2007/115819 .
  • the DC magnetron sputtering power supply connected to the graphite cathode or cathodes preferably results in an average power density at the cathode in the range from 1 to 3 Watts per square cm.
  • the HIPIMS power supply connected to the HIPIMS cathode or cathodes in the method steps B) and C) also results in an average power density in the range from 1 to 3 Watts per square cm and is operated with a duty cycle of pulse on time to pulse interval in the range from 0.5% to 4%.
  • the total area of the graphite cathodes is preferably in the range from 2 to 4 times that of the area of the HIPIMS cathode or cathodes, preferably three times as great.
  • a vacuum coating apparatus 10 for coating a plurality of substrates or workpieces 12.
  • the apparatus includes a vacuum chamber 14 of metal, which in this example has three magnetron cathodes of graphite 16, which in this example are each connected to a common DC magnetron sputtering power supply 18, and a further magnetron cathode 17 of WC + Mo which is connected to a HIPIMS power supply 19.
  • magnetron cathode will be understood to mean a cathode or target such as 16 or 17 having an associated magnetic system for generating a tunnel of magnetic field lines in the vacuum chamber in front of the respective cathode to ensure repeated collisions of electrons and the material of the cathodes for the purpose of generating ions of a material which is present in the gas phase in the chamber 14, i.e. inert gas ions and ions of the materials of which the respective cathodes are formed.
  • the workpieces 12 are mounted on a support device in the form of a table 20 which rotates in the direction of the arrow 22 by means of an electric motor 24.
  • the electric motor drives a shaft 26 which is connected to the table 20.
  • the shaft 26 passes through a lead-through 28 at the base of the chamber 14 in a sealed and isolated manner which is well known per se.
  • This substrate bias power supply 32 is shown here with the letters BPS, an abbreviation for bias power supply.
  • the BPS is preferably equipped with HIPIMS-biasing capability, as described in the EP application 07724122.2 published as WO2007/115819 , in particular, but not exclusively, with regard to the embodiment of Figs. 1 to 3 .
  • the metallic housing of the vacuum chamber 14 is connected to ground and this is at the same time the positive terminal of the apparatus.
  • the positive terminals of the DC cathode power supply 18 and the high impulse cathode power supply 19 (HIPIMS power supply 19) are likewise connected to the housing 14 and thus to ground 36 as is the positive terminal of the bias power supply 32.
  • a connection stub 40 is provided at the top of the vacuum chamber 14 (but could be located at other locations as well) and can be connected via a valve 42 and a further line 44 to a vacuum system for the purpose of evacuating the treatment chamber 14.
  • the vacuum system is not shown but well known in this field.
  • a further line 50 which serves for the supply of an inert gas, especially argon, to the vacuum chamber 14, is likewise connected to the top of the vacuum chamber14 via a valve 48 and a further connection stub 46. If a transition layer of a nitride is desired then nitrogen can be supplied via an additional gas supply system 43.
  • the cathode 17 consisting of WC (tungsten carbide) and Mo (molybdenum) may, for example, be formed from powders of WC and Mo or may comprise a segmented cathode having segments of WC and segments of Mo, the relative amounts or areas of the two components WC and Mo are selected having regard to the respective sputtering yields so that, taking account of the additional hard carbon contributed by the three graphite cathodes the proportion of W and Mo in the coating to the proportion of C in atomic percent is typically in the range (W + Mo)/C is equal to 5 to 20 %, preferably 10 to 20 % and so that the ratio of W to Mo in the coating by atomic percent is in the range from 33 to 80 % especially from 50 to 75 % and especially of around 66%.
  • the WC + Mo cathode 17 is connected to a HIPIMS cathode power supply 19.
  • Vacuum coating apparatus having a plurality of cathodes of different kinds are known in the prior art.
  • a vacuum coating apparatus is available from the company IHI Hauzer Techno Coating BV in which the chamber has a generally square shape in cross-section with one cathode at each of the four sides as shown in a horizontal cross-section through the chamber in Fig.2 .
  • This design which is admirably suited for carrying out the present process and depositing the coating in accordance with the present invention, has one side 21 designed as a door permitting access to the chamber 14.
  • the chamber is approximately octagonal in cross-section with two doors which each form three sides of the chamber. Each door can carry up to three magnetrons and associated cathodes 16, 17.
  • a typical vacuum coating apparatus includes a plurality of further devices which are not shown in the schematic drawings of this application.
  • Such further devices comprise items such as dark space shields, heaters for the pre-heating of the substrates and sometimes electron beam sources or plasma sources in diverse designs.
  • air is first extracted from the vacuum chamber 14 by the vacuum pumping system via the line 44, the valve 42 and the line 40 and the argon is supplied via the line 50, the valve48 and the connection stub 46.
  • the chamber 14 and the workpieces 12 are preheated during pump-down to drive out any volatile gases or compounds which adhere to the workpieces or chamber walls.
  • the inert gas (argon) which is supplied to the chamber is always ionized to an initial extent, for example by cosmic radiation and splits up into ions and electrons.
  • the HIPIMS cathode 17 is used for etching the workpieces which takes place in known manner in accordance with the EP patent
  • EP 1 260 603 by bombarding the workpieces with W, C, Mo and Ar ions while a high negative bias voltage is applied to the workpieces 12 of, for example, - 1200Volts. During this etching process the graphite cathodes 16 are switched off, i.e. not supplied with DC power by the power supply 18 which is itself switched off.
  • a glow discharge can be generated on the workpieces.
  • the ions W, C, Mo and Ar are attracted to the workpieces and collide there with the material of the workpieces, thus etching the workpieces.
  • the coating mode can be switched on.
  • a transition layer of W, C and Mo on the etched surface of the workpiece. This can be done by HIPMS sputtering from the WC + Mo cathode 17 using a bias voltage which is significantly lower than that used for etching, for example in the range from -100 to -300 Volts, so that there is some implantation of the respective ions into the workpiece surface thereby forming a good transition or bond layer of, for example 100nm thickness.
  • the graphite cathodes 16 are still switched off.
  • the actual coating of Me plus carbon can now be generated by simultaneous operation of the HIPIMS cathode 17 in the HIPIMS mode using the HIPIMS power supply and of the graphite cathodes using the DC power supply.
  • the bias power supply BPS 32 then remains in operation to supply a negative bias to the substrates and to prevent arcing.
  • the same bias power supply 32 copes both with DC magnetron sputtering from the graphite cathodes 16 and HIPIMS sputtering from the HIPIMS cathode 17 with no need for any form of adaptation to cope with the two sputtering modes and no need for any special synchronization of the bias voltage with the HIPIMS power pulses.
  • the simultaneous use of HIPIMS with the magnetron cathode 17 and DC magnetron sputtering from the magnetron cathodes 16 has the significant advantage that the ionization in the chamber is kept high during the HIPIMS sputtering and this beneficially effects the sputtering from the graphite cathodes and leads to the desired ratio of the sp2 bonds to the sp3 bonds in the coating.
  • the negative bias is generally maintained at a value in the range from -30 to -200 Volts although this value can drop off slightly during each HIPIMS pulse as will be explained with reference to Figs. 3 and 4 .
  • bias power supply 32 It is actually possible to dispense with a bias power supply and to allow the workpieces 12 to reach a floating potential which is ordinarily between about - 30Volts to - 40Volts. However, some form of arcing protection circuitry would normally be necessary. Naturally, the provision of the bias power supply 32 allows much improved control of the process.
  • the power supply to the cathode or cathodes causes a flux of ions of the material of the cathode to move into the space occupied by the workpieces 12 and to coat them with the material of the respective cathode.
  • the structure of the coating is influenced by the applied negative bias voltage that influences the movement of ions towards the workpieces.
  • HIPIMS cathodes In a HIPIMS mode the power which is supplied to the cathode 17 during a power impulse can be much higher than the power of a DC sputtering mode because there are substantial intervals between each pulse. However, the average power remains the same as for DC puttering.
  • the limiting constraint on the power is the amount of heat that can be dissipated at the cathode before this overheats. Accordingly, HIPIMS cathodes of about 1200square cm's surface area (rectangular cathodes of 60cm's x 20 cm' are frequently used) are generally not operated at average powers above about 20 kW.
  • the DC magnetron sputtering power supply would normally also provide a power in the range from 15kW to 20kW.
  • each power pulse can have a duration of say 200 ⁇ s the apparatus is operated with a duty cycle of 0.5 to 4 % particularly of 1 to 2 %, i.e. the ratio of the pulse on time to the pulse off time.
  • a duty cycle 0.5 to 4 % particularly of 1 to 2 %, i.e. the ratio of the pulse on time to the pulse off time.
  • WO 2007/115819 describes a solution as shown in Fig. 1 of this application in which an additional voltage source 60 is provided which is best realized by a capacitor.
  • the capacitor 62 is charged by a customary bias power supply to the desired output voltage.
  • BPS bias power supply
  • a normal bias power supply could not deliver such a peak current when it is designed for constant DC operation instead of HIPIMS operation.
  • the capacitor 62 which is charged by the bias power supply to the desired voltage in the periods between the power impulses, is able to keep the desired bias voltage at the substrates constant within narrow limits and to supply the required current which only causes a small degree of discharging of the capacitor. In this way, the bias voltage remains at least substantially constant.
  • the BPS 32 is able to maintain the bias voltage at the substrate carrier 20 within close limits and to support the relatively low flow of current when only the graphite cathodes are operating, during the pauses between sequential HIPIMS power pulses at the cathode 17 and it is also able to support the relatively high flow of current which results when the HIPIMS power supply is applying power to the HIPIMS cathode 17 in addition to the DC power being supplied to the graphite cathodes.
  • This voltage level is maintained during the operation of the graphite cathodes in the DC sputtering mode until another power impulse arises from the power supply 18 to the cathode 17 and then drops again to -40 V over the duration of the high power pulse before recharging starts again.
  • bias voltages are at much higher levels, say between less than 700 V up to 1200 V and higher.
  • the capacitor provides only a low impedance to the current flowing so that the current flowing is short-circuited through the capacitor rather than flowing through the higher impedance of the bias power supply.
  • the peak flow of ions to the substrates occurs during the power peak applied by the cathode power supply to the cathode this does not mean that the flow ceases as soon as the power peak is over. Instead it is entirely possible that the flux of ions continues, albeit at a reduced level with reduced current, during the intervals between successive power peaks, where the applied power on the cathodes is much lower.
  • arcing it is also possible for arcing to take place in the treatment chamber with the system just described.
  • the arcing further modifies various operating parameters of the system, for example the current flowing in the line 27 and the voltage across the capacitor 62.
  • detectors can be provided, such as 64, which detect the current flowing in the line 32, and 66, which detects the voltage across the capacitor and the output signals from these detectors can be fed to an arcing suppression circuit 68 which is connected to operate a semiconductor switch shown schematically at 34 in Fig. 1 .
  • the arcing suppression circuit operates to open the switch 34, thus interrupting the bias voltage present at the substrate carrier 20 and at the substrates 12 and leading to prompt extinguishing of the arc.
  • the broken line including the detector 66' shows an alternative position for the voltage detector 66, i.e. directly between the line 27 and the positive terminal of the bias power supply 32, i.e. on the other side of the switch 34 from the detector 66.
  • the position shown for the detector 66' is the preferred position.
  • the arc suppression circuit is included in the voltage source 60, it could however be a module separate from the voltage source 60 or incorporated into the bias power supply 32.
  • the two oppositely disposed cathodes 16 at the sides of Fig. 2 have magnet arrangements with centre poles of polarity "north" (N) and outside poles of polarity “south” (S) to generate the well-known magnetic tunnel of a magnetron.
  • the cathodes have the shape of elongate rectangles when viewed face on and are shown here in a cross-section perpendicular to their long axis. Instead of having SNS polarity as shown, they could have NSN polarity as shown for the magnet arrangements for the cathodes 16 and 17 at the top and bottom of Fig. 2 .
  • the two cathodes 16 and 17 at the top and bottom of Fig. 2 would then have magnet arrangements with SNS polarity.
  • the magnet arrangements can be moved in the direction of the respective double arrows 82 towards and away from the respective cathodes 16. This is an important control parameter for the operation of the HIPIMS cathodes.
  • the magnetrons to have alternating polarities going around the vacuum chamber 14. This means, with an even number of cathodes that the magnetic poles always alternate, i.e. N, S, N, S, N, S, N, S, N, S, N, S, N, S, N, S, N, S, N, S, S, S, S, S, S, S, S, S, S, S, when going around the chamber. This leads to an enhanced magnetic confinement of the plasma. A similar magnetic confinement can also be achieved if all cathodes have the same polarities, say NSN. Then it is necessary to operate with auxiliary S poles between the adjacent magnetrons to obtain a similar N, S, N, S, N arrangement around the chamber. It will be appreciated that the described arrangements only work with an even number of magnetrons.
  • FIG. 2 also shows is four rectangular coils 80 positioned like the magnets with the SNS poles or NSN poles outside of the chamber 14.
  • the coils form electromagnets and have the same polarity as the outer magnets for the respective cathodes 16, 17.
  • These electromagnetic coils 80 enable the magnetic flux in front of the cathodes 16 and inside the chamber 14, to be varied.
  • the coatings can be produced by combining carbon, evaporated from arc sources, with Mo and W evaporated by magnetron sputtering from separate Mo or WC (or simply W) targets.
  • Mo or W targets are preferred. This is less costly, as pure W targets are much more expensive, since they are not readily available in the market.
  • the Mo and W can be sputtered form one WC target in which Mo plugs are mounted. This is incidentally a form of target segmentation as referred to above.
  • ta-C coatings are a type of DLC coating
  • the WC target is run with a power of 200 W in a F1200 machine (power density: 110 mW/cm 2 ; i.e. 200 W/m if the power is related to the height of the cathode), and if a bank of 5 arc cathodes of 63mm diameter is run with a current of 60 - 80 A (which means a current density of 240-320 A/m) one obtains a coating with a deposition rate of 0,01 ⁇ m/h WC and 1 ⁇ m/h ta-C.
  • the doping level is in this case therefore approximately 1%.
  • Me-doped C-coatings by arc sputtering or HIPIMS sputtering or DC magnetron sputtering from a single graphite cathode or target having inserts or plugs of the respective metal such as Mo and/or W and/or of WC.
  • the respective free surface areas of the plugs or inserts and the of the graphite body are selected having regard to the respective sputtering yields to deliver the desired composition of the Me-doped C-coating and, if required the desired ratio of the Mo and W components in the Me-doped C-coating.
  • the pressure prevailing in the treatment chamber are typically the same as quoted above for magnetron sputtering.
  • nitride coating If a nitride coating is required this can be achieved by admitting nitrogen to the treatment chamber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Shafts, Cranks, Connecting Bars, And Related Bearings (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Claims (15)

  1. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal dans laquelle le revêtement de C à dopage Me est destiné à fonctionner dans des conditions de lubrification frontières, dans laquelle le métal est présent dans le revêtement dans une quantité de 5 à 20 atomes % et le rapport du pourcentage atomique du métal Me sur le pourcentage atomique du carbone C n'excède pas 1:4, le métal étant capable de former un sulfure de métal avec du soufre présent dans un lubrifiant et étant un mélange de W et de Mo dans un rapport de pourcentage atomique de W:Mo dans la plage de 0,5:1 à 4:1.
  2. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal selon la revendication 1, dans laquelle le rapport de W sur Mo dans le mélange est dans la plage de 1:1 à 3:1 atomes %.
  3. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal selon la revendication 1, dans laquelle le rapport de W sur Mo dans le mélange est de 2:1 atomes %.
  4. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal selon l'une quelconque des revendications précédentes, dans laquelle le rapport sp2/sp3 des liaisons carbone sp2 sur les liaisons carbone sp3 est dans la plage de 20 à 50 %, de préférence de 30 à 35 %.
  5. Utilisation d'un revêtement de carbone dopé de métal selon l'une quelconque des revendications précédentes, avec une huile contenant du soufre sous la forme d'une huile raffinée ou d'une huile raffinée contenant des additifs.
  6. Utilisation d'un revêtement de carbone dopé de métal selon l'une quelconque des revendications précédentes à une température dans la plage de 0° C à 500° C.
  7. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal selon l'une quelconque des revendications précédentes, ayant une épaisseur dans la plage de 500 nm à 10 µm.
  8. Pièce à oeuvrer ayant un revêtement de carbone dopé de métal selon l'une quelconque des revendications précédentes ayant pour composition ta-C:Mo:W ou ta-C:H:W:Mo.
  9. Procédé de déposition d'un revêtement de carbone dopé de métal selon la revendication 1 sur une pièce à oeuvrer, comprenant les étapes suivantes consistant à :
    A) préchauffer une surface d'une pièce à oeuvrer par bombardement simultané de la surface avec des ions accélérés de l'un au moins parmi des ions W et C, des ions No et C, et des ions W, Mo et C générés par une décharge de type HIPIMS dans une chambre de traitement,
    B) déposition d'une couche de transition de métal et/ou de nitrure de métal d'une épaisseur dans la plage de 20 nm à 1000 nm d'épaisseur par pulvérisation au magnétron, le métal étant au moins un parmi W et Mo,
    C) déposition d'une couche principale comprenant le revêtement de C dopé de Me par pulvérisation au magnétron utilisant l'une des configurations de cathode suivantes :
    a) une cathode de pulvérisation du type HIPIMS comprenant W, Mo et C et étant soit une cathode faite à partir des composants respectifs W, Mo et C, soit des composants WC et Mo réalisée par une procédure de frittage en métallurgie des poudres, soit encore par coulée ou par segmentation mécanique et avec une alimentation de puissance HIPIMS associée,
    b) une cathode de pulvérisation du type HIPIMS comprenant W et Mo, et une alimentation de puissance HIPIMS associée,
    c) une première cathode de pulvérisation du type HIPIMS comprenant un composant parmi W et WC et une seconde cathode pulvérisation du type HIPIMS comprenant du Mo, chaque cathode ayant une alimentation de puissance HIPIMS associée, qui peut être une alimentation de puissance commune,
    d) l'une quelconque des configurations de cathode suivantes a), b) et c) en combinaison avec une ou plusieurs cathodes en graphite, chacune avec une alimentation de puissance de pulvérisation associée en courant continu, qui peut être une alimentation de puissance commune.
  10. Procédé selon la revendication 9, dans lequel au moins l'étape de déposition C) et en option toutes les étapes de transition, comme les étapes A) et B), sont effectuées dans une atmosphère d'argon dans une chambre de traitement sous vide avec une pression d'argon dans la plage de 1 à 10-3 mbar à 10-1 mbar.
  11. Procédé selon la revendication 9 ou 10, dans lequel l'étape de prétraitement A) est effectuée en utilisant une alimentation de puissance HIPIMS et l'une quelconque des configurations de cathode a), b) et c), et avec un voltage de polarisation de la pièce à oeuvrer plus élevé que -500 V, et/ou dans lequel les étapes B) et/ou C) du procédé sont effectuées soit sans application séparée d'un voltage de polarisation à la pièce à oeuvrer avec pour résultat un potentiel de polarisation flottant de -30 à -40 V, soit avec une alimentation de puissance de polarisation connectée à la pièce à oeuvrer et adaptée à alimenter un voltage de polarisation à la pièce à oeuvrer dans la plage de -30 volts à -200 V.
  12. Procédé selon l'une quelconque des revendications 9 à 11, dans lequel la pulvérisation à magnétron utilisée dans l'étape C) comprend une pulvérisation à magnétron en courant continu utilisant une alimentation de puissance de pulvérisation de magnétron à courant continu connectée à la cathode ou aux cathodes en graphite avec pour résultat une densité de puissance moyenne au niveau de la cathode dans la plage de 1 à 3 watts par centimètre carré.
  13. Procédé selon l'une quelconque des revendications précédentes 9 à 11, dans lequel la pulvérisation à magnétron utilisée dans l'étape C) est effectuée avec une alimentation de puissance HIPIMS connectée à la cathode ou aux cathodes HIPIMS et a pour résultat une densité de puissance moyenne dans la plage de 1 à 3 W par centimètre carré, et est amenée à fonctionner avec un cycle de service concernant la temporisation sur l'intervalle des impulsions dans la plage de 0,5 % à 4 %.
  14. Procédé selon l'une quelconque des revendications précédentes 9 à 13, dans lequel l'aire totale des cathodes en graphite est dans la plage de 2 à 4 fois plus élevée que l'aire de la cathode ou des cathodes HIPIMS, de préférence trois fois plus élevée.
  15. Procédé pour déposer un revêtement de carbone dopé de métal selon la revendication 1 sur une pièce à oeuvrer, comprenant les étapes suivantes consistant à :
    A) prétraiter une surface d'une pièce à oeuvrer par bombardement simultané de la surface avec des ions accélérés de l'un au moins des ions W et C, des ions Mo et C, et des ions W, Mo et C, les ions étant générés soit par une décharge de type HIPIMS dans une chambre de traitement, soit par une décharge à magnétron en courant continu dans une chambre de traitement, soit encore par une décharge d'un arc dans une chambre de traitement,
    B) déposer une couche de transition de métal et/ou d'un nitrure de métal d'une épaisseur dans la plage de 20 nanomètres à 1000 nm d'épaisseur par pulvérisation par magnétron ou par la décharge d'un arc, le métal étant un au moins parmi W et Mo,
    C) déposer une couche principale comprenant un revêtement de C dopé de Me par décharge d'un arc depuis au moins une cathode en graphite, dans lequel, en plus de ladite cathode en graphite, des atomes de Mo, W, et en option également de C sont générés à partir de l'une des configurations de cathode suivantes :
    a) une cathode comprenant W, Mo et C, qui est soit une cathode faite à partir des composants respectifs W, Mo et C, soit à partir des composants WC et Mo, réalisée par une procédure de frittage en métallurgie des poudres, soit encore par coulée ou par segmentation mécanique,
    b) une cathode comprenant W et Mo,
    c) une première cathode comprenant un composant parmi W et WC, et une seconde cathode comprenant Mo.
EP15171849.1A 2014-06-30 2015-06-12 Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée Active EP2963145B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP15171849.1A EP2963145B1 (fr) 2014-06-30 2015-06-12 Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée
JP2015124446A JP6636728B2 (ja) 2014-06-30 2015-06-22 境界潤滑状態となる高温で動作する堆積物のコーティングおよびその方法
US14/755,073 US20150376532A1 (en) 2014-06-30 2015-06-30 Coating and Method for its Deposition to Operate in Boundary Lubrication Conditions and at Elevated Temperatures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14175063 2014-06-30
EP15171849.1A EP2963145B1 (fr) 2014-06-30 2015-06-12 Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée

Publications (2)

Publication Number Publication Date
EP2963145A1 EP2963145A1 (fr) 2016-01-06
EP2963145B1 true EP2963145B1 (fr) 2018-01-31

Family

ID=51014237

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15171849.1A Active EP2963145B1 (fr) 2014-06-30 2015-06-12 Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée

Country Status (3)

Country Link
US (1) US20150376532A1 (fr)
EP (1) EP2963145B1 (fr)
JP (1) JP6636728B2 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015119455B3 (de) * 2015-11-11 2016-11-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Vorrichtung zum Unterdrücken von Arcs in einem Elektronenstrahlerzeuger
FR3061756B1 (fr) * 2017-01-11 2019-05-10 H.E.F. Piston pour machine thermique, machine thermique comprenant un tel piston, et procedes
US10519539B2 (en) * 2017-03-24 2019-12-31 City University Of Hong Kong Method for hydrogen-free diamond-like coatings having isolated carbon particle embedded within
JP6476261B1 (ja) 2017-10-17 2019-02-27 株式会社神戸製鋼所 成膜方法
DE102018213534A1 (de) * 2018-08-10 2020-02-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Vorrichtung und Verfahren zur Herstellung von Schichten mit verbesserter Uniformität bei Beschichtungsanlagen mit horizontal rotierender Substratführung
CN111962020A (zh) * 2020-08-11 2020-11-20 东莞市普拉提纳米科技有限公司 一种新型ta-c涂层工艺
EP3964604A1 (fr) * 2020-09-03 2022-03-09 IHI Ionbond AG Cda dopé pour plaque bipolaire (bpp) et applications tribologiques
CN113154036A (zh) * 2020-11-13 2021-07-23 纳峰真空镀膜（上海）有限公司 活塞环及制造方法
WO2022101416A1 (fr) * 2020-11-13 2022-05-19 Nanofilm Vacuum Coating (Shanghai) Co., Ltd. Segments de piston et procédés de fabrication
CN113481474A (zh) * 2021-06-29 2021-10-08 苏州光昛智能科技有限公司 一种无机电致变色薄膜的溅射镀膜方法
KR102647411B1 (ko) * 2021-11-29 2024-03-14 한국생산기술연구원 열간등방가압 탄소 표면처리 용기 및 이를 이용한 열간등방가압 탄소 표면처리 방법
CN114231924A (zh) * 2021-12-14 2022-03-25 海南大学 一种用于改善轴承橡胶密封圈耐磨损性能的表面处理方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5786068A (en) * 1991-05-03 1998-07-28 Advanced Refractory Technologies, Inc. Electrically tunable coatings
US5458927A (en) * 1995-03-08 1995-10-17 General Motors Corporation Process for the formation of wear- and scuff-resistant carbon coatings
JP3355306B2 (ja) * 1997-09-30 2002-12-09 帝国ピストンリング株式会社 ピストンリング
DE10124749A1 (de) 2001-05-21 2002-11-28 Wolf-Dieter Muenz Kombiniertes Beschichtungs Verfahren magnetfeldunterstützte Hochleistungs-Impuls-Kathodenzerstäubung und Unbalanziertes Magnetron
JP4360082B2 (ja) * 2001-12-17 2009-11-11 住友電気工業株式会社 非晶質炭素被膜の製造方法及び非晶質炭素被覆摺動部品
US7820293B2 (en) * 2005-08-18 2010-10-26 Nv Bekaert Sa Substrate coated with a layered structure comprising a tetrahedral carbon coating
GB2437080B (en) 2006-04-11 2011-10-12 Hauzer Techno Coating Bv A vacuum treatment apparatus, a bias power supply and a method of operating a vacuum treatment apparatus
US20090065350A1 (en) * 2007-09-07 2009-03-12 Nanochip, Inc. Filtered cathodic arc deposition with ion-species-selective bias
DE102010002687C5 (de) * 2010-03-09 2015-09-10 Federal-Mogul Burscheid Gmbh Verfahren zur Beschichtung zumindest der Innenfläche eines Kolbenrings sowie Kolbenring
KR20130069621A (ko) * 2010-05-07 2013-06-26 가부시키가이샤 니콘 도전성 슬라이딩막, 도전성 슬라이딩막이 형성된 부재 및 그 제조 방법
DE102011116576A1 (de) * 2011-10-21 2013-04-25 Oerlikon Trading Ag, Trübbach Bohrer mit Beschichtung
EP2628817B1 (fr) * 2012-02-15 2016-11-02 IHI Hauzer Techno Coating B.V. Article revêtu d'acier martensitique et procédé de formation d'un article revêtu d'acier
DE102012007796A1 (de) * 2012-04-20 2013-10-24 Amg Coating Technologies Gmbh Beschichtung enthaltend Si-DLC, DLC und Me-DLC und Verfahren zur Herstellung von Beschichtungen
CN102965619A (zh) * 2012-12-07 2013-03-13 中国地质大学（北京） 一种多元金属掺杂无氢类金刚石碳膜的制备方法
BR102014007893B1 (pt) * 2014-04-02 2022-03-22 Mahle International Gmbh Elemento deslizante, motor de combustão interna e processo de obtenção de elemento deslizante

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP6636728B2 (ja) 2020-01-29
US20150376532A1 (en) 2015-12-31
JP2016027197A (ja) 2016-02-18
EP2963145A1 (fr) 2016-01-06

Similar Documents

Publication Publication Date Title
EP2963145B1 (fr) Revêtement et procédé de son dépôt pour l'utilisation aux conditions de lubrication interfacielles et à température augmentée
EP2628822B1 (fr) Composants de roulements isolés et roulements
US9115426B2 (en) Coated article of martensitic steel and a method of forming a coated article of steel
CN109267007B (zh) 用于在工件上沉积无氢四面体非晶碳层的装置和方法
US6033734A (en) Method of coating metallic and ceramic substrates
JP6297049B2 (ja) コーティングを有するコンポーネントおよびその製造方法
JP6388868B2 (ja) コーティングを有するコンポーネントおよびその製造方法
JP4300762B2 (ja) 炭素膜被覆物品及びその製造方法
CN103874780A (zh) 具有涂层的钻头
Ghantasala et al. Magnetron sputtered thin films based on transition metal nitride: structure and properties
JP4670751B2 (ja) 摺動部材
JP3542735B2 (ja) なじみ性に優れた積層皮膜及びその形成方法
Moore et al. Nanostructure and Nanocomposite Thin Films
JP2013119633A (ja) 摺動部材

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HOVSEPIAN, PAPKEN E.

Inventor name: EHIASARIAN, ARUTIUN PAPKEN

Inventor name: TIETEMA, ROEL

Inventor name: DOERWALD, DAVE

17P Request for examination filed

Effective date: 20160704

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015007683

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0014020000

Ipc: C23C0014060000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 14/34 20060101ALI20170714BHEP

Ipc: C10M 103/04 20060101ALI20170714BHEP

Ipc: C23C 14/16 20060101ALI20170714BHEP

Ipc: C23C 14/32 20060101ALI20170714BHEP

Ipc: H01J 37/34 20060101ALI20170714BHEP

Ipc: C23C 14/06 20060101AFI20170714BHEP

Ipc: C23C 14/35 20060101ALI20170714BHEP

Ipc: C23C 14/02 20060101ALI20170714BHEP

INTG Intention to grant announced

Effective date: 20170808

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

Ref country code: CH

Ref legal event code: NV

Representative=s name: DR. GRAF AND PARTNER AG INTELLECTUAL PROPERTY, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 967457

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015007683

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180131

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 967457

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180131

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180430

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180531

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180430

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180501

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015007683

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20181102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180630

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180612

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180612

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180612

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180131

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150612

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230628

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230622

Year of fee payment: 9

Ref country code: CH

Payment date: 20230702

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230829

Year of fee payment: 9